CN101280362B

CN101280362B - Recovery method of platinum catalyst in membrane electrode of waste fuel batter with proton exchange film

Info

Publication number: CN101280362B
Application number: CN2008100114543A
Authority: CN
Inventors: 徐洪峰; 赵红; 卢璐
Original assignee: Dalian Jiaotong University
Current assignee: Dalian Jiaotong University
Priority date: 2008-05-15
Filing date: 2008-05-15
Publication date: 2010-06-23
Anticipated expiration: 2028-05-15
Also published as: CN101280362A

Abstract

The invention proposes a recycling method of platinum catalyst in the membrane electrode of the waste proton exchange membrane fuel cell, and the purpose of the recycling method is to enhance the recycling rata of the noble metal in the catalyst layer. The recycling method of the invention comprises the steps that catalyst on the membrane electrode is shaken out from the catalyst layer by using an ultrasonic cell crasher firstly, then the majority of the catalyst is recycled, and the rest of the catalyst is put into a high-pressure autoclave. Solid polymer electrolyte is dissolved by using solvent and separated from the catalyst, and then the catalyst is separated from carbon, PTFE and other components by using a centrifugal machine. The recycling method has the obvious advantage that the recycling rate of the noble metal catalyst is high.

Description

The recovery method of the platinum catalyst in the membrane electrode of waste fuel batter with proton exchange film

Technical field

The invention belongs to the Proton Exchange Membrane Fuel Cells technical field, particularly the recovery technology of platinum catalyst in the membrane electrode of waste and old Proton Exchange Membrane Fuel Cells.

Background technology

The membrane electrode of Proton Exchange Membrane Fuel Cells (PEMFC) is made of anode diffusion layer, anode porous carbon-coating, anode catalyst layer, dielectric film, cathode catalysis layer, negative electrode porous carbon-coating and seven layers of hot pressing of cathode diffusion layer usually together.Wherein Catalytic Layer is to carry platinum or Pt-Ru/C catalyst and solid polymer electrolyte by carbon to constitute, and Catalytic Layer can be attached to the porous carbon-coating, also can be attached on the dielectric film.Membrane electrode is worked in fuel cell behind the certain hour, owing to be subjected to the gathering of external pollution or catalyzer self, and the decay of film and breaking, cause fuel cell not use.But the physico-chemical property of noble metal platinum in the Catalytic Layer of waste and old fuel cell and ruthenium etc. does not change, and just catalytic activity has reduced.It is reclaimed, be not only and save limited precious metal resources effective approach, also can obtain good economic benefit.

At present, the method for precious metal has burning method and chloroazotic acid pickling process in the traditional recovery fuel cell membrane electrode.Burning method is with catalyzer in the Catalytic Layer and solid polymer electrolyte, so the carbon in the porous carbon-coating and PTFE scrape, high temperature incineration makes carbon, solid polymer electrolyte and PTFE be converted into carbonic acid gas, water and other vapor-phase fluoride.Its shortcoming is that fluorochemical has severe toxicity, severe contamination working space and atmospheric environment.And the chloroazotic acid pickling process, owing to many catalyzer are wrapped up by solid polymer electrolyte, so catalyst recovery yield is not high, about 60-70%.

Summary of the invention

The present invention proposes a kind of new catalyst recovery method, to improve noble metal recovery rate in the Catalytic Layer, promptly utilize ultrasonic cell disruptor that the catalyzer on the membrane electrode is shaken from Catalytic Layer, reclaim most of catalyzer, remaining part is then put into autoclave, makes the solid polymer electrolyte dissolving, with catalyst separating, utilize the density difference of catalyzer and carbon, PTFE at last, separating catalyst and other component.Technical scheme of the present invention is: the recovery method of the platinum catalyst in the membrane electrode of waste fuel batter with proton exchange film, it is characterized in that described recovery method comprises that ultrasonic oscillation reclaims and dissolving-centrifugal separation reclaims, the method that described ultrasonic oscillation reclaims platinum catalyst is: the electrode or the film that contain Catalytic Layer are peeled off with membrane electrode: waste membrane electrode was put into ethanol or Virahol immersion 5-10 minute, electrode and ionogen are peeled off, taken out the electrode or the film that contain Catalytic Layer; 2) electrode or the film that will contain Catalytic Layer is divided into small pieces, puts into the container that ethanol or Virahol are housed; 3) shredder head of ultrasonic cell disruptor is put into container, start ultrasonic wave, shook 30-40 minute; 4) stop ultrasonic cell disruptor, treat that solution in the container is static after, reclaim the catalyzer precious metal and measure noble metal amount from container bottom; Described dissolving-centrifugal separation is: will scrape from electrode or film together through platinum catalyst and the solid polymer electrolyte that ultrasonic oscillation does not reclaim, the mixture that scrapes is put into the autoclave of the ethanol water mixed solution that is equipped with 1: 1, the amount of putting into of mixture is 3%～8%, under 250 degrees centigrade, constant temperature 2-3 hour, make the solid polymer electrolyte dissolving, solution is taken out in the cooling back from autoclave, separate with whizzer, the catalyzer precious metal is deposited in the sedimentator bottommost.

Advantage of the present invention is: recovery method is simple, precious metal rate of recovery height.

Embodiment

The waste membrane electrode that 1 area is 100mm * 300mm is done the recovery of Catalytic Layer precious metal.The catalyzer of this membrane electrode is that 50% carbon carries platinum (Pt/C), and carrying capacity is 1mgPt/cm ², entire electrode has Pt/C catalyzer 600mg, and platinum is 300mg.After membrane electrode put into aqueous isopropanol and soak 5-10min, electrode and film layering, taking-up is with film and electrode separation.The electrode that will contain catalyzer is cut into the small pieces of 50mm * 50mm, puts into the container that Virahol is housed, and the amount of Virahol is as the criterion to flood the electrode small pieces.The ultrasonic wave of ultrasonic cell disruptor is taken place to start ultrasonic wave in the head insertion aqueous isopropanol, begin concussion, shut down behind the concussion 40min.After treating that the interior solution of container is static, the sedimentary catalyzer of container bottom is collected, place oven dry in the drying baker, claim to such an extent that weight is 400mg.Entire electrode has Pt/C catalyzer 600mg, also has the 200mg catalyzer not to be recovered.The carbon and the PTFE of remaining catalyzer on the electrode and part porous carbon-coating are together scraped with blade, the powder that scrapes put into ethanol and water volume ratio are housed is 1: 1 autoclave, be heated to 250 degree, insulation 2h, open autoclave, take out mixing solutions and pour in the centrifuge tube, centrifugation catalyzer and other impurity in supercentrifuge (rotating speed is greater than 200 rev/mins).After the separation, the catalyzer of centrifuge tube bottom is taken out oven dry, weighing obtains containing the catalyzer 240mg of a small amount of carbon dust.The catalyzer that obtains for twice is together put into muffle furnace, under the 500-600 degree, burn 1h, remove the carbon in the catalyzer, obtain pure platinum 292mg, the platinum rate of recovery is 97.3%.

Claims

1. the recovery method of the platinum catalyst in the membrane electrode of waste fuel batter with proton exchange film, it is characterized in that described recovery method comprises that ultrasonic oscillation reclaims and dissolving-centrifugal separation reclaims, the method that described ultrasonic oscillation reclaims platinum catalyst is: the electrode or the film that contain Catalytic Layer are peeled off with membrane electrode: waste membrane electrode was put into ethanol or Virahol immersion 5-10 minute, electrode and ionogen are peeled off, taken out the electrode or the film that contain Catalytic Layer; 2) electrode or the film that will contain Catalytic Layer is divided into small pieces, puts into the container that ethanol or Virahol are housed; 3) shredder head of ultrasonic cell disruptor is put into container, start ultrasonic wave, shook 30-40 minute; 4) stop ultrasonic cell disruptor, treat that solution in the container is static after, reclaim the catalyzer precious metal and measure noble metal amount from container bottom; Described dissolving-centrifugal separation is: will scrape from electrode or film together through platinum catalyst and the solid polymer electrolyte that ultrasonic oscillation does not reclaim, the mixture that scrapes put into the autoclave that volume ratio is 1: 1 an ethanol water mixed solution is housed, the amount of putting into of mixture is 3%～8%, under 250 degrees centigrade, constant temperature 2-3 hour, make the solid polymer electrolyte dissolving, solution is taken out in the cooling back from autoclave, separate with whizzer, platinum catalyst is deposited in the sedimentator bottommost.